Fine fluorescence and absorption spectra of hypericin in a polymer matrix at a temperature of 4.2 K

Monochromatic photoexcitation and selective registration in bands of purely electronic S₁↔S₀ transitions resulted in fine fluorescence and absorption (fluorescence excitation) spectra of hypericin in polyvinylbutyral at a temperature of 4.2 K. Vibration analysis of the spectra is done and conclusions are made about the form of many normal vibrations. It is found that the formation of intramolecular hydrogen bonds in the hypericin structure has a substantial effect on the relative position of the electronic vibrational levels of the pigment molecule. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina ave., Minsk 200072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 539–545, July–August, 1998.     

Infrared multiphoton excitation of polyatomic molecules

Results of investigations of the process of multiphoton excitation of polyatomic molecules by CO₂-laser radiation are presented. The mechanism of formation of the profiles of IR absorption bands of polyatomic molecules is discussed. New experimental methods of investigation of relaxation processes at high levels of vibrational excitation of molecules in the ground and triplet states are considered. For vapors of polyatomic molecules and their mixtures with foreign gases, the quantitative characteristics of the collisional exchange and the vibrational-energy transfer as well as the rates of intercombinational conversion ⇛ and triplet-triplet transfer are presented and their dependences on the vibrational-excitation level are discussed. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 675–693, September–October, 1998.     

The width of the rotational contour of vibrational and vibronic bands of complex molecules in the gas phase as a temperature indicator

From the independence of the contour of spectral density of the rotational (orientation) correlation function of a rigid molecular top of arbitrary symmetry on temperature in the frequency scale based on the reduced time of rotational orientation relaxation and from the near independence of the rotational contour of vibrational and vibronic absorption bands of dipole transitions in the same coordinates in a model of “regular diffusion” of the transition oscillator with a classically rotating rigid molecular top, it is suggested that it is possible to use the halfwidth of the contour for estimation of temperatures. Data are presented on the halfwidth of 48 contours of bands of A, B, and C types at this frequency for 12 compounds for a temperature range of from units to 500 degrees of absolute temperature measured experimentally and (for low temperatures) calculated by the quantum theory. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 312–317, May–June, 1997.     

Methods for fine-tuning frequencies of absorption of actinide complexes to frequencies of laser generation lines

On the basis of analysis of relationships relating, among themselves, the positions of bands in the spectra of electron and IR absorption of uranyl complexes in solutions and the donor ability of neutral ligands, the possibility is shown for fine-tuning frequencies of absorption of complexes to frequencies of argon- and CO₂-laser generation lines and using them in the development of methods of control over chemical reactions involving actinides. Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 420–422, May–June, 1999.     

Calculation and analysis of the frequencies of normal vibrations of 2,3-Di-O-nitro-methyl-β-D-glucopyranoside

A calculation of the frequencies and forms of the normal vibrations of the 31-atom molecule 2,3-di-O-nitromethyl-β-D-glucopyranoside has been performed. Particular emphasis has been placed on the interpretation of the strongest bands in the spectrum of 2,3-di-O-nitro-methyl-β-D-glucopyranoside, which are due to vibrations of the nitrate groups. The present work has been reported at the IV International Congress of theoretically competent chemists, Jerusalem (Israel), July 7–12, 1996. B. I. Stepanov Institute of Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 724–728, November–December, 1997.     

Transformation of radiation-induced defects responsible for theF-band of absorption in NaF crystals subjected to irradiation with light and annealing

It has been found that the F-band of optical absorption which is observed in ψ-irradiated NaF crystals consists of three overlapping bands. The band at 345 nm of width 40 nm is independent of the impurity composition of the crystals; it disappears upon exposure to radiation at 345 nm and appears again upon annealing at 460±15 K for 15 min. This band is correlatable in intensity with the superfine structure of an EPR spectrum. The width (65–110 nm) and the spectral position (355–375 nm) of the second band depend on the impurity composition of the crystal. The band of width 90–110 nm at 320–325 nm disappears upon annealing and appears after exposure to light simultaneously with the disappearance of an EPR signal. It is established that the band at 345 nm is caused by quasimolecules based on fluorine atoms, that at 355–375 nm is triggered by F-centers with a different impurity composition near the haloid vacancy, and the band at 320–325 nm owes its appearance to F-centers in a negatively charged state (F′). Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 849–853, November–December, 1999.     

Li ion conduction on plasticizer-added PVAc-based hybrid polymer electrolytes

Poly(vinyl acetate), poly(vinylidene fluoride–hexafluoropropylene), lithium perchlorate salt, and the different plasticizer-based gel polymer electrolytes were prepared by solvent-casting technique. The structural and the complex formation have been confirmed by X-ray diffraction spectroscopic analysis. Thermal stability of the different plasticizer-added electrolyte films has been analyzed by means of thermogravimetric analysis. Ionic conductivity of the electrolyte samples has been found as a function of temperature and the plasticizers. Among the various plasticizers, ethylene carbonate-based complexes exhibit maximum ionic conductivity value of the order of 10⁻⁴ Scm⁻¹. Finally, the microstructure of the maximum ionic conductivity sample has been depicted with the help of scanning electron microscope analysis.     

Simulation of the influence of the polymer conformation,orientation, crystallinity,and stretching on its IR absorption spectrum

Using cis-1,4-polyisoprene as an example, the influence of the conformation and orientation of the polymer chain on its polarization absorption spectra has been simulated. It has been shown that if a change in the orientation of the polymer chain leads to a monotonic change in the intensities of the absorption bands with their maxima positions remaining unchanged, then changes in the polymer chain conformation additionally cause a shift and the appearance of new absorption bands. According to the results of the calculation of the vibrational spectra, the inversion of the IR dichroism of the absorption bands of polymers is associated with the conformation transition. We simulate the influence on the IR absorption spectrum of the degree of crystallinity of cis-1,4-polyisoprene, in which the amorphous and amorphous-crystalline states are considered as a mixture of noninteracting polymer chains, where each state is characterized by a certain ratio of conformers. Likewise, the changes in the IR absorption spectrum of cis-1,4-polyisoprene under its stretching have been investigated. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 727–733, November–December, 2005.     

Fluorescence and absorption of polystyrene exposed to UV laser radiation

We show that when polystyrene is exposed (for 15–60 sec) to a UV laser light beam (λ = 248 nm), its absorption and luminescent properties change significantly. In the irradiated polymer, optical centers are formed with absorption bands in the 280–460 nm region and fluorescence bands in the 330–520 nm region. We have established the chemical structure of the optical centers for fluorescence of polystyrene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 54–58, January–February, 2006.     

IR spectroscopic manifestations of hydration of poly(diphenyl sulfophthalide) during its storage

IR spectroscopy measurements show that films of poly(diphenyl sulfophthalide) (PDSP), a cardo polymer, interact with atmospheric moisture during storage at room conditions. A total of 15 absorption bands were isolated in spectra of PDSP hydrated during storage, which belong to sorbed water and hydrolysis products. A number of absorption bands (within 1500–1800 cm⁻¹ and 980–1100 cm⁻¹) were obtained by subtracting the spectrum of the film after heating from that of the initial hydrated film. At least six individual bands in the region of the O-H bond stretching vibration were isolated by decomposing a broad complex band (3700–2000 cm⁻¹) into Gaussian components. The isolated bands were tentatively assigned based on the available literature data and quantum-chemical calculations of the characteristics of a number of complexes of a diphenyl sulfophthalide model compound with water molecules. The IR spectra and energies of the hydrogen bonds formed were calculated at the B3LYP/6-311G(d, p) level. In particular, the absorption bands at 1010 and 1079 cm⁻¹ were assigned to the symmetric stretching vibrations of the S=O bonds in the −SO₃⁻ anion, the 1062-cm⁻¹ absorption band, to ν(C-OH), and the absorption bands at 3646, 3586, and 3475 cm⁻¹, to complexes of water with sulfophthalide cycles of the polymer. After a long storage, PDSP largely transforms into a polymeric oxonium salt, and its spectrum becomes similar to that of a polymeric salt prepared by alkaline hydrolysis. A general mechanism of the interaction of PDSP with water is proposed, according to which the hydrolysis of the sulfophthalide cycles (SPC) by sorbed water yields new hydrophilic groups, sulfoacid, and hydroxyl groups. A further sorption of water by the sulfoacid results in its ionization and the formation of various hydroxonium forms. Sorption and hydrolysis are reversible processes: water is desorbed and the SPC is recovered when the polymer is heated to 100–150°C, as can be judged from an increase in the intensity of the S=O bond vibrations of the sulfophthalide cycle at 1352 and 1192 cm⁻¹. The possibility of using strongly hydrated PDSP for manufacturing proton-conducting membranes is discussed.     

Absorption and fluorescence of 9,10-diiodoanthracene in undegassed solutions

A procedure for producing 9,10-diiodoanthracene that is an alternative to the known procedure is described. The spectra of absorption and fluorescence in hexane, carbon tetrachloride, and polymethylmethacrylate are measured at 22°C. The quantum yield of undegassed liquid solutions in hexane and carbon tetrachloride in excitation at the maximum of the 0←0 band is practically the same and is equal to 0.018. In excitation in shorter-wave vibrational bands, it is different for different solvents and decreases noticeably as the frequency of the exciting light increases. The decrease in the yields is explained by the existence of a fast nonradiative process from hot (Franck-Condon) vibrational S₁-states capable of competing with vibrational relaxation. A possible scenario of this approach is discussed. Institute of Molecular Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 197–200, March–April, 1999.     

Analysis of glucopyranoside trinitrate IR spectrum

The IR spectrum of 4-O-methyl-2,3,6-tri-O-nitromethyl-β-D-glucopyranoside has been interpreted in detail for the first time based on complete calculation of the normal vibration frequencies and absolute intensities of its IR absorption bands and a comparison of them with the corresponding experimental data. The results indicate that the location of the nitrates in cellulose nitrates can be determined experimentally from separate components of complicated absorption bands in the ranges 1700–1600 and 900–800 cm⁻¹ of the IR spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 43–51, January–February, 2008.     

Kinetics of fluorescence polarization for solid bichromophore solutions in intense pulse excitation

The kinetics of fluorescence polarization in intense pulse excitation of solid disordered solutions of bichromophores that consist of complex molecules of two types between which there can be inductiveresonance transfer of electron-excitation energy is theoretically investigated. Variants of fluorescence excitation by single pulses and pulse trains are considered. The lifetime of the fluorescence of a given solution increases with the intensity of the exciting pulses. The possibility of controlling the duration of fluorescence attenuation for donor molecules incorporated into the bichromophores by the action of luminescence radiation at the frequency of acceptor-molecule absorption on the solution is demonstrated. Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii Vol. 65, No. 4, pp. 546–550, July–August, 1998.     

Device for UV irradiation of blood with a disposable blood flow system

A device for extracorporal irradiation of blood by UV light with λ=300–400 nm is described. A disposable blood flow system with a specially profiled polymer cuvette is proposed. Mixing of blood during irradiation ensures uniform irradiation of blood cells passing through the cuvette, which makes it possible to enhance the healing effect of the procedure. B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 289–292, March–April, 1999.     

Extra-liganding effects in Zn-octaethylporphyrin solutions in a temperature interval of 300-77 K

It is established experimentally for the first time that Zn-octaethylporphyrin in a solution of dried methyl cyclohexane is in unliganded form in the temperature interval of 293-77 K. This form is characterized by the shortest-wave position of absorption and luminescence spectra, the independence of the degrees of fluorescence and phosphorescence polarizations from the excitation wavelength, and high phosphorescence time (τ_T=126 μsec) and quantum yield (φp=0.085) at 77 K. Adding electrodonor components to the methyl cyclohexane or going over to alcohol-containing polar media leads to the formation of a monoliganded form of ZnOEP, for which we observe a bathochromic shift of ≈150–350 cm⁻¹ for Q(0,0) absorption and luminescence bands, a splitting of ≈50–100 cm⁻² for the Q(0, 0) absorption band, and phosphorescence quenching (τ_T=60 μsec, φp=0.05-0.03 at 77 K). The effects revealed are explained by a decrease in the symmetry of a ZnOEP molecule in extra liganding and by an increase in the probability of nonradiative activation for a T₁-state due to the extra ligand being involved in the exchange of electron-excitation energy and to the enhancement of a spin-orbital coupling as a result of the disturbance of the planarity, of a macrocycle. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 900–907, November–December, 1998.     

A method for continuous control of the refractive index of liquids in capillaries

An interference method for controlling the refractive index of liquids pumped through a capillary is considered. The liquid is sounded by two systems of interference bands, the period of which differs by an insignificant value prescribed by the condition of nonius coincidence. An analytical expression is obtained to calculate the refractive index of the liquid controlled in automatic reading of the interference patterns. Institute of Electronics, National Academy of Sciences of Belarus, 22 Logoiskii Trakt, Minsk, 220841, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 832–835, November–December, 1999.     

Remote spectrophotometry as applied to determination of the degree of mineralization of peat soils in polesie

Regression relations between the first main component, slope of the SBC curve towards the wavelength axis, and the degree of mineralization of peat soils are established from experimental data. Errors in determination of peat soil productivity are estimated using different spectral indices. For practical use it is recommended to measure the spectral brightness coefficients of peat soils in the 0.50–0.75 μm range. B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 102–106, January–February, 1998.     

Luminescence of human blood serum in the longwave spectral region

An investigation is made of the absorption, fluorescence, and fluorescence excitation spectra of human blood serum whole and diluted with a sodium-phosphate buffer solution. Time characteristics of the longwave serum luminescence are obtained. The quantum yield of background fluorescence upon excitation by radiation with λexc=500 is found to be 0.5%. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 433–436, May–June, 1999.     

Color and optical characteristics of carbon coatings produced by magnetron sputtering

The color parameters of carbon coatings deposited by magnetron sputtering of a graphite target onto substrates of stainless steel without a sublayer and with a titanium sublayer are calculated. By numerical modeling, the refractive indices and extinction coefficients for the titanium sublayer and carboniferous film as well as the volume content of titanium dioxide in the sublayer are determined. Physico-Technical Institute of the Academy of Sciences of Belarus, 4, Zhodinskaya St., Minsk, 220141, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 374–385, May–June, 1997.     

New feature of the phosphorescence of copper complexes ofmeso-tetraarylporphyrins

Introduction of methyl groups in orthopositions of phenyl rings of a Cu-meso-tetraphenylporphin (Cu-TPhP) molecule is shown to lead to a substantial decrease in the diffusivity of the spectrum of low-temperature (77 K) phosphorescence. It is found that the long-lived (580 μsec) and short-lived (0.7 μsec) components of Cu-TPhP phosphorescence differ in emission and absorption (phosphorescence-excitation) spectra and belong to two forms of molecules. The phosphorescence spectrum of the predominant form with small τ_p is diffuse, while its absorption spectrum is shifted slightly in a bathochromic manner. The phosphorescence spectrum with large τ_p is structural and is similar to the spectrum of Cu-meso-tetrakis-(ortho-tolyl)porphin. The difference is attributed to the nonplanarity (saddle distortion) of a Cu-TPhP molecule in the lower triplet state in the case of the form with small τ_p. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus; e-mail: llum@imaph.bas-net.by. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 743–747, November–December, 1999.